Catalytic polymerization of unsaturated, polymerizable compounds with catalysts comprising adducts of phosphorous esters with alpha-diketones



United States Patent 3,324,200 CATALYTIC POLYMERIZATION OF, UNSATU-RATED, POLYMERIZABLE COMPOUNDS WITH CATALYSTS COMPRISING ADDUCTS 0FPHOSPHGROUS ESTERS WITH a-DIKETONES Horst Leithauser, Marl, Germany,assignor to Chemische Wei-Ire Huts Alrtiengesellschaft, Marl,Germany, acorporation of Germany N0 Drawing. Filed Oct. 22, 1965, Ser. No. 502,278Claims priority, application Germany, Apr. 2, 1963, C 29,544; Nov. 20,1964, C 34,425 3 Claims. (Cl. 260865) My application *Ser. No. 339,356,filed Jan. 22, 1964, now Patent No. 3,285,994, relates to a process forthe catalytic polymerization of unsaturated polymerizable compoundsinvolving the use of an initiator system which is an adduct of anoxygen-containing compound of trivalent phosphorus with up to an equalmolecular equivalent, based upon said phosphorus compound, of anu-diketone. Said adduct can be used alone or together with a peroxidiccatalyst. The initiator system is used in an amount within the rangefrom 0. 01 to 3'0 and preferably within the range from 0.02 to 12% byweight based upon the weight of the polymerizable compound.

Oxygen-containing compounds of trivalent phosphorus, suitable for theinitiator system are the mono-, diand triesters of the phosphorous acid(I), the monoand diesters of the phosphonous acid (II), and the estersof the phosphinous acid (III). They are employed together withpreferably equimolecular quantities of an a-diketone of the Formula IVaor IVb.

O R OR!!! RI, RI!" RI Bl R/IP RI!!! RIIII C O RIII [I H [I H OR" OR Rm 0O O I II III a IV 0 In the above formulae R and/ or R represent hydrogenor alkali metal or alkyl, aryl, cycloalkyl or aralkyl;

R", R'", R"": are identical or dissimilar aliphatic, cycloaliphatic,aromatic or araliphatic residues which may be halogenated or jointly maybe part of a ring.

It has now been found that esters, nitriles and amides of unsaturatedacids, vinyl aromatic compounds and mixtures of esters of unsaturatedacids with vinyl aromatic compounds can be catalytically polymerized bymixing the polymerizable composition under polymerization conditionswith an initiator which is an adduct within the range from 1:1 to 1:2produced by reacting in a molecular ratio within the range from 1:1 to1:4 a carbonyl compound selected from the group consisting ofa-diketones, ketones and aldehydes with a 1:1 adduct of the generalformula RIH |C RHII o 0 oft 191v in which R stands for a member selectedfrom the group consisting of hydrogen, alkali metals, and alkyl,cycloalkyl, aryl and aralkl groups which may be halogenated, R standsfor a member selected fromthe group consisting of alkyl, cycloalkyl,aryl, aralkyl and OR groups which may be halogenated, R" stands for amember selected from the group consisting of the alkyl, cycloalkyl,aryl, aralkyl, O-alkyl, O-cycloalkyl, O-aryl and O-aralkyl groups whichmay be halogenated, R' and R"" each stands for a member selected fromthe group consisting of the alkyl, cycloalkyl, aryl and aralkyl groupswhich may be halogenated, and in which the pairs R and R" and R' and R""may belong to the same ring, at least one of R, R and R" being such agroup as will assure that the compound of said general formula'isanester.

An example of a suitable initiator in accordance with the invention isthe a-diketone "adduct obtainable as described in J. Am. Chem. Soc., 84(1962), pages 1317-1318, by addingan ot-diketone such as 'diacetyl'inathree-fold molecular excess dropwise to, e.g., triethylphosphite at roomtemperature with stirring and under an atmosphere of nitrogen'and thencontinuing the stirring under the same conditions'for atime and thenseparating the excess of the carbonyl compound from the reaction mixtureby vaporization under vacuum. v

If one starts with the preformed 1: 1-adiketone adduct, one then addsthe a-diketone, ketone or aldehyde with stirring under nitrogen at 20-25C.'11ntil one attains a molecular ratio of adduct to carbonyl compoundwithin the range from 1:1 to 1:4, preferably 1:3.

One may also make the 1:1 adduct in the usual way and then withoutisolating it react it as described above.

In instances in which color (e.g., diacetyl) or odor (e.g., diacetyl,acetaldehyde, benzaldehyde) may be objectionable a smaller amount of thecarbonyl compound preferably is used corresponding to the 2:1 adduct.Otherwise the amount'of carbonyl compound is so chosen that the actionof the resulting initiator system gives the desired polymerizationresult. I

Examples of suitable unsaturated polymerizable compounds arehydrocarbons, esters, ethers, nitriles and amides which contain at least'one polymerizable double bond, also mixtures known as unsaturatedpolyester resins of unsaturated polyesters with compounds that arepolymerizable thereto and other mixtures of polymerizable compounds thatare capable of mixed polymerization. Examples that may be named arestyrene, vinyltoluene, divinylbenzene, methacrylic acid methyl ester,methacrylic acid ethyl ester, methacrylic acid butyl ester,acryl-onitrile, tert. butylacrylamide, and especially mixtures of thesevinyl compounds with unsaturated polyesters of e.g., maleic acid,fumaric acid, itaconic acid with glycols such as ethylene glycol,1,3-propylene glycol and 2-ethylhexane diol.

In the following examples unless otherwise specified commercialunsaturated polyester resin, which have a viscosity of UP according tothe German industrial standard No. 53015 and which contain styrene asthe monomer polymerizable thereto, are used. The unsaturated polyesterresins are referred to hereinafter in the usual manner by theabbreviation UPER.

The add'ucts V-VIII referred to in the following examples were preparedas described above from (1) Diacetyl and triethylphosphite (adduct V);

(2) Diacetyl, pentanedione-(2,3) and triethylphosphite (adduct VI); 7

/ (3) Diacetyl and phenylphosphonous acid bis chloro-iso-propyl ester)(adduct VII) (4) Diacetyl, benzaldehyde and triethylphosphite (adductVIII).

Example 10 Example 1b The same mixture as in Example 1a with the benzoylperoxide omitted gelled in 20 minutes and heating at C. gave an evenharder test body.

Example 2 9.5 g. of UPER and 0.2 g. of benzoylperoxide paste werestirred together at room temperature. 0.5 g. of ad- 4 Example 7 0.2 g.of benzoylperoxide paste (50%) was added to 10 g. of the unsaturatedpolyester resin of Example 6 and then 0.5 g. of adduct V was added. Themixture duct VI was added and the resulting mixture gelled in o 12minutes. A hard, clear test body was produced by gelled at roomtemperature 3 mmutes' At 80 It heatingat 800 gave a hard, clear,non-adhesive test body.

Example 3 Example 8 5% by weight of adduct VII was added to a UPER 0.2cc. of cobalt naphthenate solution (20%) and 0.4 and the mixture gelledin 3 minutes. The gel was heated of cyclohexanon'peroxlde (50%) wereadded to 10 at giving a hard, clear test body. when the Same of theunsaturated polyester resin of Example 6. Upon amount of adduct VII wasadded to a mixture of UPER the further addition of 0.5 g. of adduct VIIIthe mixture and 2% of benzoylperoxide paste (50%) the resulting gelledat room tempelature m 15 mmutegartd hardened mixture gfiued immediatelyto a clear, non-adhesive test body. In a similar test ad- 15 duct V wassubstituted as the initiator and the mixture Example 4 gelledimmediately and hardened equally smoothly. 0.5 g. of adduct VIII wasadded to 10* g. of UPER. Example 9 The mixture gelled after beingstirred at room temperature for 4 hours. By heating at 80 C. a clearhard parts by Welght 9 acrylomtnle W treated under nolmficky test bodywas produced nitrogen at 50 C. with 1 part by welght of adduct V. Afterabout 30 minutes the polymer began to separate. Example 5 After severalhours the reaction was practically complete. A comparative samplewithout adduct remained 10 g. of UPER, 0.2 cc. of cobalt naphthenatesolution unchanged- (20%) and 0.4 cc. of cyclohexa on pergxide (50%) Inother polymenzation experiments under otherw1se \were stirred at roomtemperature. 0.5 g. of adduct V was Similar Conditions except theaddition of P of :added and the mixture gelled immediately and hardenedbenloyl PerOXide the P y began to spal'ate .to a clear, non-adhesivetest body. Adduct VIII was subafter about minutes. After about 1 hourspontaneous :stituted for adduct V in a similar mixture and the result-Polymerization took Pl with Partial P ing mixture gelled in 6 minutesand also hardened to a 30 111 Similar teXtS wlthollt adduct addltlon butWith clear, non-adhesive test body. benzoyl peroxide the polymer beganto separate only after about 1 hour and the spontaneous poylmerizationExample 6 occurred after about 1 hour and 20 minutes. 0.5 g. of adduct Vwas added to 10 g. of a flame re- Example 10 sistant unsaturatedpolyester resin (styrene content: 25%; Mixture of 67 parts of maleicacid monoallyl ester and stabilizer concentration: 0.02% hydroquinone;composi- 33 parts of styrene were treated under the conditions tion ofpolyester: lmol of 1,4,5,6,7,7-hexachl-oro-bic clo s ecified in thefollowing table with adducts V to VIII y p a 4 [2,2,1] 5 heptene 2,3dicarboxyhc acid anhydride, and/or benzoyl-peroxide. The gelling timesand the prop- 1 mol of furnaric acid, 1.05 mol of glycol and 1.05 molerties of the polymers are shown in the table.

TABLE I Weight of Weight of Weight of Gelling No. Mixture Adductbenzoyltime, Remarks peroxide minutes 10 Not gelled in 4 hours.

15 Hardened at 80 C. 46 Do. 17 Hardened completely at room temperature(exothermic) 6 43 Hardened completely, strongly exothermic.

of diglycol). The mixture gelled at room temperature in Example 11 5mmutes; At the f formed a h'ard, clear For the following tests shown inthe following table nomadhesw? I? y- S1m11a1 Sample Yvlth adducta-diketone and triethylphosphite and a commercial un- VIII as theinitiator gelled in 79 minutes. ThlS also upon t t d l e t r re in(Vestopal H) based upon heatlng at gave a hard, c e non-adhesive testphthalic acid, fumaric acid and propylene glycol mixed body. with 33% byweight of styrene were used.

TABLE II No. UPER, Paste, Adduct, Adduct, Adduct, Gel.

g. g.BP g. 1:1 g.2:1 g. 1.5:1 time, Remarks 1-. Not gelled in 4 hrs. 2Weak heating. 3-.." Heating. 4-.

7 Weak heating.

1 Benzoylperoxide paste (50%).

By heating at 80 C. test samples 2-7 gave hard, clear and colorless testpieces.

I claim:

1. Process for the catalytic polymerization of esters, nitriles andamides of unsaturated acids, vinyl aromatic compounds and mixtures ofesters of unsaturated acids with vinyl aromatic compounds whichcomprises mixing the polymeriza-ble composition under polymerizationconditions with an initiator which is an adduct within the range from1:1 to 1:2 produced by reacting in a molecular ratio within the rangefrom 1:1 to 1:4 a carbonyl compound selected from the group consistingof oc-diketOnCS, ketones and aldehydes with a 1:1 adduct of the generalformula RIII O=C RIIII O i 011G911 in which R stands for a memberselected from the group consisting of hydrogen, alkali metals, andalkyl, cycloalkyl, aryl and aralkyl groups which may be halogenated, Rstands for a member selected from the group consisting of the alkyl,cycloalkyl, aryl, aralkyl and OR groups which may be halogenated, R"stands for a member selected from the group consisting of the alkyl,cycloalkyl, aryl, aralkyl, O-alkyl, O-cycloalkyl, O-aryl and O- aralkylgroups which may be halogenated, R and R"" each stands for a memberselected from the group consisting of the alkyl, cycloalkyl aryl andaralkyl groups which may be halogenated, and in which the pairs R and R"and R and R" may belong to the same ring, at least one of R, R and R"being such a group as will assure that the compound of said generalformula is an ester.

2. Process as defined in claim 1 in which a peroxidic catalyst is addedto the reaction mixture.

3. Process as defined in claim 1 in which the polymerizable compositionis a mixture of an unsaturated polyester and a compound which ispolymerizablc thereto.

No references cited.

MURRAY TILLMAN, Primary Examiner. J. T. GOOLKASIAN, Assistant Examiner.

1. A PROCESS FOR THE CATALYTIC POLYMERIZATION OF ESTERS, NITRILES ANDAMIDES OF UNSATURATED ACIDS, VINYL AROMATIC COMPOUNDS AND MIXTURES OFESTERS OF UNSATURATED ACIDS WITH VINYL AROMTIC COMPOUNDS WHICH COMPRISESMIXING THE POLYMERIZABLE COMPOSITION UNDER POLYMERIZATION CONDITIONSWITH AN INITIATOR WHICH IS AN ADDUCT WITHIN THE RANGE FROM 1:1 TO 1:2PRODUCED BY REACTING IN A MOLECULAR RATIO WITHIN THE RANGE FROM 1:1 TO1:4 A CARBONYL COMPOUND SELECTED FROM THE GROUP CONSISTING OFE-DIKETONES, KETONES AND ALDEHYDES WITH A 1:1 ADDUCT OF THE GENERALFORMULA